JPS6225756A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sharpness by incorporating in a silver halide photographic sensitive emulsion a photosensitive compound to release a dye same in color as a dye released by a diffusion-resistant coupler when this compound and said coupler react with the oxidation product of a color developing agent. CONSTITUTION:The compound to be incorporated in the silver halide emulsion is endowed with the following properties; (i) It releases a diffusion-resistant dye same in color as the dye released by the diffusion-resistant coupler when this compound and this coupler react with the oxidation product of a color developing agent, (ii) it properly diffuses during a development processing stage. Both dyes produced by this compound and the coupler form a color image together with each other. In the zones in which the color image is not formed with the diffusion-resistant coupler this compound remains nonreacted, and since it has diffusivity, it forms an unsharp image,and consequently, a color negative image and an unsharp positive image are produced, and the image can be made sharp.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention consists of 1. The present invention relates to a photosensitive silver halide color photographic material (hereinafter simply referred to as "photographic material"), and particularly to a photographic material capable of automatically forming a color image and an unsharp mask.

(Prior art) As a photographic material capable of forming color images and unsharp masks to obtain color images with excellent sharpness, a physical development nucleus-containing layer containing a diffusion-resistant coupler and a scavenger for oxidized color developing agents are used. A photographic material is disclosed in French Patent No. 2.260.124, in which a photosensitive silver halide emulsion layer containing a diffusion-resistant coupler is laminated in sequence.

A preferred method for obtaining a color negative image and an unsharp positive image using the photographic material is that after exposure, first color development is performed without containing a silver halide solvent, and color development is performed at night to obtain a color negative image, and then halogenated A method for obtaining an unsharp positive image by performing physical color development using a second color developer containing a silver solvent is disclosed.

However, in order to obtain a color negative image, this photographic material undergoes a color development reaction in the exposed area, and in order to obtain an unyielding positive image, C is dissolved in the unexposed area. B3: It is necessary to cause a reaction. Therefore, in order to prevent the diffusion of the oxidized color developing agent into the physical development nucleus-containing layer during formation of a color negative image, a scavenger of the oxidized color developing agent is placed between the two layers containing the diffusion-resistant coupler. It is essential that the

That is, in the absence of the scavenger, some of the oxidized color developing agent generated in the exposed area will diffuse into the physical development nucleus-containing layer, where a color development reaction will occur to produce a negative image. Buboji 1'
↑ cannot be obtained.

Furthermore, since three layers including the sky/jar containing layer are essential, it is difficult to make the film thin, and from this point of view as well, it is difficult to improve sharpness.

Further, as disclosed above, this method requires that color development be performed twice using two color developing solutions. If we were to carry out color development only once using only a color developing solution containing a silver halogenide solvent, there would be a need for color development to obtain a color negative image and for supplying silver ions to the physical development nucleus-containing layer.・Silver chloride j: It is good to have <Ii'i control over the production of the body. If this control breaks down and the 111 objects are produced in excess, less color negative images will be produced, and the j
: As a result of excessive diffusion into one physical development nucleus layer, an/? - Since a puboji image is generated, the desired color negative image and Unyaap mask image cannot be obtained, and the purpose cannot be achieved.

(Objective of the Invention) The object of the present invention is to solve the above-mentioned drawbacks of the prior art. That is, a first object of the present invention is to provide a photographic material capable of obtaining an image with improved sharpness by generating a color negative image and an unsharp positive image.

A second object of the invention is to provide a photographic material which provides a sharpened image with fewer essential layers for sharpness enhancement.

A third object of the present invention is to provide a photographic material in which a good color negative image and an unsharp positive image can be completely formed by one color development.

(Structure, Effects of the Invention) As a result of intensive research to achieve the above object, we have discovered the object of the present invention and how it can be achieved using a photographic material having the following structure. That is, the photographic material of the present invention is a light-sensitive silver halide color photographic material comprising a diffusion-resistant coupler combined with a light-sensitive silver halide emulsion. ) The diffusible coupler and the color developer: The pigment is substantially the same color as the pigment produced by the reaction with the oxidized form of the crude drug, or the color is substantially the same color as the pigment produced by the reaction between the diffusible coupler and the oxidized form of the crude drug. : is a compound that diffuses, and iii)
Contains a compound that produces a diffusion-resistant dye of substantially the same color as the dye produced by the reaction between the diffusion-resistant coupler and the oxidized color-developing agent. Features.

In addition, in the present invention: 'C, during the developing process, J, abnormally diffusing is a copy of the present invention] (Specifically, in the developing process using the material; , preferably 5 μm, but at least 30 wt % of the i′11 remains in the photographic material after processing.

Further, diffusion resistance means that the diffusion property is relatively small compared to the diffusion property of the compound according to the present invention described above, and the diffusion property in the drawing process is preferably 5 μm or less, more preferably 2 μm or less. It means something made up.

This invention: Let's think about it in more detail.

First, 1) a dye of substantially the same color as the dye produced by the reaction between the 6f diffusive coupler and an oxidized form of a color developing agent, or a precursor thereof; a diffusion-resistant compound, and iii) a diffusion-resistant dye having substantially the same color as the dye formed by the reaction of the diffusion-resistant coupler with the acid monomer of the color developing agent upon reaction with the oxidized form of the color developing agent; The compound that produces (hereinafter referred to as the compound of the present invention) will be explained.

The reaction between the uninvented compound itself, the compound of the present invention, and the r-2 compound of a color-forming visual imaging agent (the resulting diffusion-resistant dye forms a color-forming form with the above-mentioned diffusion-resistant coupler; an oxidized form of the crude drug). The compound of the present invention itself and the diffusion-resistant dye produced by the reaction of the compound of the present invention with the oxidized form of a color developing agent are actually the same color as the dye produced by the reaction with the above-mentioned dye. It means that the dye has its main absorption in the main absorption wavelength range of the dye produced by the reaction between the diffusion-resistant coupler and the oxidized color developing agent.

However, the hue of the compound itself is different from that of the dye produced by the reaction between the above-mentioned diffusion-resistant coupler and the oxidized form of the color developing agent, but during the development process, hydrolysis 1
) Refers to a compound whose colors A and U become substantially the same color due to reactions such as 7.

It takes i】? By using the T; compound, it is possible to prevent a decrease in sensitivity when the compound of the present invention is added to a photosensitive silver halide emulsion layer.

The above-mentioned compound of the present invention has a property of reacting with an oxidized product of a color developing agent. Therefore, in areas where a color image is produced by the reaction of the oxidized form of the color developing agent with the diffusion-resistant coupler, the compounds of the present invention will also react with the oxidized form of the developing agent to form a diffusion-resistant dye similar to the J1 diffusible coupler. However, this dye forms a color image together with the diffusion-resistant dye produced by the reaction 1 between the above-mentioned diffusion-resistant coupler and the oxidized color developing agent.

On the other hand, the compound of the present invention remains unreacted in areas where no color image is produced by the diffusion-resistant coupler. As a result, the color image produced by the diffusion-resistant coupler and the unreacted compound of the present invention have an inverse relationship to the color i'i! ii1 image, that is, if the former is negative 1Ifif&, the latter will form a positive image. Moreover, since the unreacted compound of the present invention has moderate diffusivity, it produces an unreacted image, that is,
An unsharp mask image will be formed.

Moreover, as described above, the compound of the present invention forms an unsharp mask image in an unreacted state, and also contributes to the formation of a color image when reacted with an oxidized product of a color developing agent.

As a result, unlike the conventional unsharp mask method, the difference in color density that makes up the color image hardly changes, so there is no large drop in gamma. The interimage effect can be used as a tr effect.

Examples of the reaction that the compound of the present invention undergoes with an oxidized color developing agent include coupling and cross-oxidation/DC 17.

In addition, the compound of the present invention can be used as a dye itself or in the body before it, and also reacts with an oxidized product of a color developing agent to form a raw dye, but it also reacts with an oxidized product of a color developing agent to form a raw dye. Reaction: It may be possible to form a new C dye part, or it may not form a new dye part, and the precursor part may be developed for 1 minute before the reaction. 8. It may remain as a dye portion after the chemical process.

The compounds of the present invention include the following types in terms of their functions.

Type I On color development: Due to the coupling with the oxidized form of (;, the dye moiety that the compound of the present invention has in advance or its precapsule is substantially combined with the dye moiety generated during the processing step. A compound (pigment-forming type) that produces a pigment part of the same color in one place and makes it resistant to diffusion.

This type can be further classified into the following types.

Type 1-1 Coupling with an oxidized form of a color developing agent causes the compound of the present invention to lose its preexisting dye moiety or its precursor moiety, and the new tc dye moiety or its precursor moiety is developed. A compound that forms a pigment part that is substantially the same color as the pigment part that should be present after the treatment process and is resistant to diffusion.

Here, the mechanisms by which the dye moiety that the compound of the present invention has in advance disappears include, for example, when the dye moiety separates as a diffusible dye that can flow out of the photographic material system, and when the dye structure decomposes and disappears. For example, when it is colored.

type! -2 Coupling with an oxidized form of a color developing agent does not eliminate all of the dye moiety or its precursor moiety that the compound of the present invention already has, and furthermore, the dye moiety or the precursor moiety is newly added to the compound of the present invention. A compound that forms a portion of color X that is substantially the same color as the dye portion that is to be formed after the development process, and also diffuses +. Therefore, this type of compound proboscis is a newly formed dye part as a result of complation with an oxidized form of a developing agent, at the intersection of a preexisting dye part or a dye part originating from its precursor. It also has (which results in a diffusible dye (
Add-on type).

Type ■ Compounds of the present invention do not lose all of their preexisting dye moieties or their precursor moieties due to camping with the oxidized product of the color developing agent, and have excellent wave resistance without forming new dye moieties. Compound that converts to 1rit.

Type ■ A compound that becomes resistant to diffusion through cross-oxidation with the oxidized form of a color developing agent.

Each of the above types will be explained in more detail.

Type I-1 compounds include, for example, the following general formula (1
Examples include compounds represented by -1).

General formula (1-1) % formula % In the formula, 1 to 1 are coupled with the oxidized developing agent to form Lin
It is an organic residue that can release the J-B1 moiety according to the amount of the oxidized developing agent and form a coupling dye, and a group that connects Linklima A1 and 81, B
, is an organic residue? clothe

Specific examples of A1 include, for example, phenols, naphthols, 5-pyrazolones, pyrazolotriazoles,
Examples include pyrazolotetrazoles, pyrazolopenzimidazoles, indacilones, a/ruacetanilides, and the like.

For example, LinJ can be used. Here, -N'thousand is a nitrogen-containing heterocyclic residue, such as imidoyl succinate, imidoyl phthalate, pyridoyl, imidazolyl, imidasilonyl, penzimidazolyl, hydantoyl, thionidine dantoyl, triazolyl, penztriazolyl, urazolyl, Examples include 2,4-dioquinoxasilyl, 2,4-dioxothiazolyl, thiadiazolyl, and tetrazolyl.

When Linkl is a chromophore such as -N=N-, B is preferably an aryl group or a heterocyclic group, and when Linkl is not a chromophore, it is a dye (e.g., azo, anthraquinone, etc.). , azomethine, indophenol, indoaniline, etc.) or a precursor thereof.

Preferably, as a dye precursor, an auxochrome (e.g. hydroxyl, Amitsunosha) is used as a dye precursor.
By protecting the inside with a hydrolyzable group (for example, an acyl group or an alkoxyoxalyl group), the main absorption wavelength can be reduced to 5 nm.
The above examples include those shifted to the shorter wavelength side.

The compound represented by the general formula (1-1) according to the above 'yD configuration is B1, AI Link, B
1 as a whole can be a dye or a precursor thereof.

The compound represented by the general formula (1-1') is given a saga that moderately diffuses during the development process, and in the case of 81-dye dyes or their precursors, the dyes generated due to these are removed from the system. and coupling: 'i: In order to prevent diffusion with the dye formed from i, an alkali-soluble group such as a carboxyl group, a sulfo group, a hydroxyl group, a sulfamoyl group, and an itie1e'-[alkyl group The diffusivity before and after the reaction may be balanced by appropriately introducing a group that lowers the diffusivity, such as the following.

Compounds belonging to this type (r/lIt are denoted by j below).

Examples of the compound of 2<02 NO2 I-2 include the compounds represented by -■-2 below.

(r-2) D, -A2, and Dl represent dye moieties or their precursor moieties; There will be no departure from A2.

A specific example is the above-mentioned specific example of A1.

Examples include the colors mentioned above as examples of B1 and their precursors. Further, A2 may be removable at the cup position upon coupling. The releasable group may be a dye or a precursor, but need not be a dye or a precursor.

Furthermore, the compound represented by the general formula (1-2) is given the property of moderate (·ζ diffusion during development processing, and the compound represented by the general formula (:l-
In order to make the dye formed as a result of the coupling of the compound in 2) with the oxidized form of the herbal drug, an alkali-soluble group such as a carboquine group, a sulfo group, a hydroxyl group, a sulfamoyl group, and an alkali-soluble group, such as Diffusivity before and after the reaction may be balanced by appropriately introducing a group that reduces diffusivity, such as an alkyl group.

For example, an alkali-soluble group that can be separated during coupling or a group containing an alkali-soluble group can be bonded to the coupling position of A2.

Specific examples of all compounds belonging to this type include the following.

SO2Cl(,5O2N(C4H9)2l) Examples of compounds of type (1) include compounds represented by the following general formula.

General formula CI) -D2 In the formula, D2 has the same meaning as D1 in general formula (1-2), and the same ones are exemplified.

W represents a compound residue that couples with the oxidized form of the developing agent but does not form a dye due to the coupling.

W may be used for reactions (e.g. oxidation reactions,
(elimination reaction) (e.g., alkyl groups such as methyl group and butyl group) and bisalkylcarbamoyl-aryloxymethane-based or bisalkylcarnoζmoy-arylthiomethane-based compound residues. It will be done.

In the general formula (n), D2 may be present at the WO coupling position as a part of a group that does not cause the reaction that migrates to the dye, or may be bonded to a position other than the coupling position.

Specifically, the compounds belonging to this type (1,
1) Among the upper concrete polymer compounds belonging to this type, compound (10) and compound (12) are derived from the methylene moiety of a β-diketomethylene compound (generally, by campling)
It is a compound substituted with a group that leaves.

However, according to the study by the present inventors: C, β-ketomethylene anilide compounds such as the above-mentioned compound (5) shown in 91j are certainly active point S L, pleasure-type compounds, but compound (10
) and (12) (β-diketomethylene dialkylamide type compounds do not cause an elimination reaction, probably because the leuco compound obtained by coupling with an oxidized color developing agent is stable). That's the headline.

Examples of compounds of type (1) include those represented by the following general formula (1).

General formula CI) Fun -D3 In the formula, D3 has the same meaning as n in the monomer formula (1-2), and examples thereof include the following.

Fun, 'i, is an organic group that has the function of reacting with the oxidized product of a color developing agent to diffuse the compound represented by the general formula CI), and includes a group having a no-hydroquinone nucleus and a group having a catechol nucleus. It will be done.

A specific example f11 of the compound belonging to the type is shown below.

OH (]8) OH○I ( The compounds of the present invention described above are synthesized according to general synthesis methods, but there are two main routes. One is to synthesize the dye part in advance and then synthesize the dye part. The moiety of the exemplified compound ((
2), (3), (4).

(5), (7), (8), (10),
(ii) , (12) , (13) , (14)
, (+6), (17).

(18) etc. are synthesized using this method.

Another synthesis method is to obtain the dye moiety by diazo coupling in the final step of the exemplified compounds (1) and (
15) is synthesized by K in this way.

Further, in the case of a dye precursor, it can be obtained, for example, by acylating an auxochrome after forming the dye.

Next, as representative compounds of the above compounds (1) and (2)
) is described below.

Synthesis of Compound (11) 1-Hydroxy 2- prepared by the reaction of toquine-2-naphthoic acid phenyl ester and p-phenetidine
31 g of p-ethoxynaphthanilide and 600 m of pyridine
Unexamined Japanese Patent Publication No. 1989-1983 where the temperature is 10° or less and the temperature is 10° or less.
Synthesized by the method of No. 33141 Synthesis Example D-4 Lt5-nitro-2-1)-sulfophenethylsulfonylaniline sodium salt 439 was dissolved in sodium nitrite 7.69% in 10% hydrochloric acid.
It is obtained by adding a diazotized solution at 5° or less using a method for coupling. The resulting blue-black target substance is reconstituted with alcohol. Parent ion beak and dye analysis in mass spectrometry (C, I-I).

N) confirmed that it was the desired product.

Synthesis of Compound (2) 1-Hydroxy-1-r)-aminophenoquine-2 obtained by hydrogenating 1-hydroquino-4-nitrophenoquine-2-n-butylnaphthamide in ethyl acetate in the presence of Raney nickel at atmospheric pressure. - 500 g of butylnaphthamide
Dissolved in mQ of acetonitrile, to which 9 m of pyridine was dissolved.
Add Q and while stirring at 200℃, synthesize L according to synthesis fiJ of No. 55-331-11 Synthesis 5ij D-1.
Ethylsulfamotl-5-N,N-dimethylaminosulfonamide-4-1:2-(2(4-chlorosulfonylphenyl)ethylsulfonyl)-4-nitrophenyl7zo-1-su7)-lua 9. ! / Gradually add. It takes about 30 minutes to finish adding everything, but after that, the mixture is stirred at room temperature for 2 hours and then boiled under reflux for 30 minutes to react. complete it. After draining and washing with hexane, a sandy powder is obtained. The parent ion peak in mass spectrometry and elemental analysis confirmed that it was the target product.

The photographic material of the invention comprises a diffusion-resistant coupler and a compound of the invention in combination with a type 6 photoactive silver halide emulsion as described above.

Here, the diffusion-resistant coupler is photosensitive silver halide emulsion 1.
The compound of the present invention is preferably contained in the silver halide emulsion layer, but it is not essential that it be contained in the same layer as the diffusion-resistant coupler. .

The amount of the compound of the present invention to be used is 0.01 to 1 mole of the diffusion-resistant coupler used in combination with the compound.
．． 00 mol is preferred, particularly 0.05 to 0.60 mol. Further, as the method for adding it, the same method as that for the diffusion-resistant coupler described later can be used.

The silver rogenide used in the photosensitive silver rogenide emulsion used in the present invention includes silver bromination, silver iodobromide, silver iodochlorobromide, silver chlorobromide, 15 and 15. Any silver oxide may be used. Silver halide grains are cubic, octahedral,
It may have a regular crystal shape such as a tetradecahedron, or it may have an irregular crystal shape such as a sphere or a plate. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed. 1. Silver halide grains may consist of a uniform phase inside and on the surface, or may consist of different phases.

The silver halide grains used in the silver halide emulsion of the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains.

The silver halide emulsion of the present invention may have any grain size distribution.

°°Emulsions with a wide grain size distribution (referred to as polydisperse emulsions)
You can also use an emulsion with a narrow grain size distribution (heavy!
(referred to as "FL cutting") may also be used. What is a monodisperse emulsion? , 18! When the standard deviation of the distribution of grain size is divided by the average particle size, the (& is less than 0.15. Here, the particle size is spherical. In the case of spherical logs, the diameter is In the case of grains of other shapes, the diameter is shown when the five projected images are converted into a circular image of the same area. Polydisperse emulsions and monodisperse emulsions may be used alone or in combination.

Silver halide emulsions may be chemically sensitized.

Furthermore, it can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. A single sensitizing dye may be used, but two or more? May be used in combination. In addition to the sensitizing dye, the emulsion contains a supersensitizer, which is a dye that itself does not have a spectral sensitizing effect or a compound that does not substantially absorb visible light, and which enhances the sensitizing effect of the sensitizing dye. It's okay.

Various hydrophilic colloids including gelatin are used as binders for the silver halide emulsion according to the present invention. Gelatin includes not only gelatin but also derivative gelatin, and derivative gelatin includes a reaction product with gelatinic acid anhydride, a reaction product between gelatin and incyanate, or a compound having gelatin and an active) rogen atom. reaction products, etc. are included. The acid anhydrides used in the reaction with gelatin include, for example, maleic anhydride, phthalic anhydride, benzoic anhydride, acetic anhydride, isatoic anhydride, cono-phosphoric anhydride, etc., and the isocyanate compounds include: For example, phenyl incyanate, r'
-Bromophenyl isocyanate, p-chlorophenylisocyanate, p-tolyl isocyanate, p-nitrophenyl isocyanate, naphthylinocyanate, and the like.

Furthermore, examples of compounds having an active halogen atom include benzenesulfonyl chloride, p-methoquinobenzenesulfonyl chloride, p-7 enoxybenzenesulfonyl chloride, p-bromobenzenesulfonyl chloride, 'p-)luenesulfonyl chloride, m-nitrobenzene. Sulfonyl chloride, m-sulfobenzoyl dichlorite, naphthalene-β-sulfonyl chloride, p-chlorobenzenesulfonyl chloride, 3-
Nito0-4-7mi/benzenesulfonyl chloride, 2
-carboxy-4-bromobenzenesulfonyl chloride, m-carboxybenzenesulfonyl chloride, 2
-Amino-5-methylpene-pinosulfonyl chloride, phthalyl chloride, p-nitropensoyl chloride, benzoyl chloride, ethylchlorocarbonate-
and 70yl chloride.

In addition to the above-mentioned derivative gelatin and dual photographic gelatin, colloidal albumin, if necessary, is used as a hydrophilic colloid to prepare a silver halide emulsion.
Agar, gum arabic, dextran, alkyl acids, cellulose derivatives such as cellulose acetate already hydrolyzed with an acetyl content of 19 to 26, polyacrylamide, imitated polyacrylamide, casein, such as vinyl alcohol-vinyl anoacetate. Urethane carbonate such as coholimer, 'i2, c is/vinyl alcohol polymer containing anoacetyl group, polyvinyl alcohol-polyvinyl pyrrolidone, hydrolyzed polyvinyl acetate, white matter or saturated unarylated protein and vinyl group It is also possible to use polymers obtained by polymerization with monomers having the following: polyvinylpyridine, polyvinylamine, polyaminoethyl methacrylate, polyethyleneimine, etc.

The silver halide emulsion of the present invention can be used for various purposes such as coating aid, anti-banding, improvement of slipperiness, emulsification dispersion, prevention of adhesives, and improvement of photographic properties (e.g. development acceleration, high contrast, sensitization). It may contain various known surfactants.

That is, U.S. Patent No. 2.240.472, U.S. Patent No. 2.83
No. 1,766, No. 3,158.48゜1, No. 3,21
No. 0,191 No. 3,294,540, No. 3,507,
No. 660, British Patent No. 1.012. ．． No. 195, same +,'
+) No. 22,878, 1,1.7 '1,290-
No. 1.198,450, U.S. Patent No. 2,739,8
No. 91, No. 2.823, 123, No. 1,179,29
No. 0, No. 1,198,450, No. 2.7.39,89
No. 1, No. 2,823,123, No. 3.058,101
No. 3.415.6-i No. 9, No. 3.666. -1
No. 78, Tsukasa 3,756,828, Eito! vI permission 1, 3
No. 97,218, +43,113,816, 3.4
No. 11,413, No. 3,473,174, No. 3,34
No. 5,974, No. 3.726,683, No. 3,843
, 368, Belgian Patent No. 731.126, British Patent No. 1,138,514, Belgian Patent No. 1,159,825, Belgian Patent No. 1.
, 374,780, U.S. Patent No. 2.271,623,
No. 2,288,226, No. 2,944,900, No. 3.235,919, No. 3.671,247, No. 3
, No. 772,021, No. 3.589,906, No. 3,
666. ．． No. 178, 3.7s No. 4,924, West German Patent Application No. OL 31,961,683, and Japanese Unexamined Patent Publication No. 1973
-117414, No. 50-59025, Japanese Patent Publication No. 40-378, No. 40-379, and No. 43-13822. 1st row is Zabonin (steroid type)
, alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl or alkylaryl ether polyethylene glycols, polyethylene glycol sorbitan esters, polyalgylene glycol alkyl amines or amides,
polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars,
Similarly, nonionic surfactants such as urethanes or ethers, tritinopenoid saponins, alkyl carboxylates, alkylbenzene sulfonates, alkylnaphthalene sulfone b tx , alkyl sulfates, alkyl phosphate esters, N-acyl- Carboxy, sulfo group, phosphor group, 5ifi' such as N-alkyl tauric acid, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxine ethylene alkyl phosphates, etc.
Anionic surfactants containing acidic groups such as ester groups and phosphate ester groups; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphate esters, alkyl betaines, amine imides, and amine imides. Cationic surfactants such as alkylamides/salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary anthonium salts such as pyridium, imidazolium, and sulfonium or sulfonium salts containing aliphatic or heterocycles. In addition to the above-mentioned surfactants, silver halide emulsions in which a development accelerator can be used include West German Patent Application (0LS) 2.002,87.
No. 1, No. 2,445,611, No. 2,360,878
It may contain imidazoles, thioethers, selenoethers, etc., which are described in No. 1, British Patent No. 1,352,196, etc.

The light-diffusive coupler is preferably contained in the above-mentioned light-sensitive silver halide emulsion layer, and examples of its combination include, for example, blue-, green-, and red-sensitive silver halide emulsions with yellow, magenta, and cyan diffusion-resistant couplers. sexual couplers are applied respectively.

The diffusible coupler preferably has a new oil group (for example, 2,4-di-t-amylphenoxyalkanamide group) in its molecule so as not to diffuse into the photographic constituent layers.

Coupler to silver ion:? j L 4 equivalent or Vi2
Either equivalence is acceptable. In addition, colored couplers have the effect of color correction, or +ij due to development inhibition during development.
It may also contain couplers that release J agents (so-called DIR couplers).

Further, some couplers may be used in which the product of the coupling reaction is colorless.

As the yellow coupler, a known open-chain ketomethylene coupler can be used. Among these, benzoylacetanilide-based and piparoylacetanilide-based compounds can be advantageously used. Specific examples of yellow couplers that can be used include U.S. Pat.
No. 17438, No. 51-102636, Special Publication No. 1977-
No. 19956, No. 51-33410, No. 51-107
Although it is described in No. 83, No. 47-19031, etc.,
Particularly preferred yellow couplers include the following compounds.

Cα) CJCα'Cl21'125 CI- et al. OOfi C) h CL (16) 9L Pyrazolone compounds, indacylon compounds, cyanoacetyl compounds, etc. can be used as magenta coloring couplers, and virasicon compounds are particularly advantageous. .

A specific example of a magenta color-forming coupler that can be used is disclosed in U.S. Pat.
．． No. 600,788, No. 3,062゜053, No. 3.
5 ] 9. = No. 129, valve, Te Kaisho 49-11163
No. 1 No. 56-29236, No. 57-94752,! It is written in Samurai Kounuma No. 48-27930, etc., and the lid is small, but t:
):ζ Preferred couplers include the following compounds.

F・7...Bagota S'O C Otsu (12) 1- (2,4,6-trichlorophenyl)
-3-(3-acrylamidobenzamide)-4-pyrazolyl-5-oxo-2-pyrazoline and n-butyl acrylate 20:800 copolymer latex impregnated with the magenta coupler (2). As the cyan color-forming coupler, phenolic compounds, naphthol compounds, etc. can be used, and specific examples thereof include U.S. Pat. No. 2,423,730 and U.S. Pat.
No. 93, No. 2,895,826, JP-A-117-1983
No. 422, Japanese Patent Registration No. 127513, etc. (although particularly preferred cyan couplers include:
The following compounds may be mentioned.

0H t (9) Of(
For colored magenta couplers, for example, US Pat.
, No. 801,171, No. 3,519.429, and Japanese Patent Publication No. 48-27930, particularly preferred colored magenta couplers are the compounds shown below.

:t) t (5nt Colored cyan couplers are described, for example, in British Patent No. 1,084,480, Japanese Patent Publication No. 55-32461, etc., but particularly preferred colored cyan couplers include the following compounds. can be mentioned.

Two or more of the above various couplers may be contained in the same layer. Further, the same compound may be contained in two or more different layers.

To introduce the coupler into the silver halide emulsion layer, known methods such as those described in US Pat. No. 2,322,027 can be used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl 7-phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl 7-phosphate), citric acid esters C example, t ld' acetyl citrate tributyl acid), benzoate esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), etc., or organic solvents with a boiling point of about 30°C to 150°C, e.g. lower alkyl acetates such as ethyl acetate, butyl acetate, propionic acid. After being dissolved in ethyl, secondary butyl alcohol, methyl isophyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used.

When the coupler has a carboxylic acid or sulfonic acid group, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

These couplers are generally added in an amount of 2.times.1 F" to 5.times.10" moles, preferably 1.times.10" to 5.times.10" moles per mole of silver in the silver halide emulsion layer.

Furthermore, DIR compounds can be used in the photographic material of the present invention, such as U.S. Pat.
, 615,506, JP-A-52'-82424, JP-A-54-145135, JP-A-57-154944, JP-A-51-161 =l 1, etc. A particularly preferable DI
For R compound list, it is possible to list the following compounds.
,・Hito1, H3 C-3) 2H5 L In addition, examples of anti-staining agents that can be effectively used in the photographic material of the present invention include, for example, U.S. Pat. Particularly preferred antifouling agents include the following compounds.

■H- Antistatic agents used in the present invention include diacetylcellulose, styrene perfluoroalkylridium maleate copolymer, and alkali salts of reaction products of styrene-maleic anhydride copolymer and p-aminebenzenesulfonic acid. etc. are valid. Examples of matting agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers. Furthermore, it is also possible to use colloidal silicon oxide. - Examples of the latex added to improve the physical properties of the film include copolymers of acrylic esters, vinyl esters, etc. and other monomers having ethylene groups. Examples of gelatin dressing agents include glycerin and glycol compounds, and examples of thickeners include styrene-sodium maleate co-M and combined CL 7.
/l/Kirch=/l/x-Tyl-maleic acid copolymer and the like.

As supports for photographic materials made using silver cogenide emulsions prepared as described above, such as baryta paper, polyethylene paper, polypropylene synthetic paper, etc.
Glass, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate,
Examples include polystyrene, and these supports are appropriately selected depending on the intended use of each photographic material.

These supports are subjected to a subbing process if necessary.

After exposure, a photographic material prepared using the silver halide emulsion according to the present invention can be developed by a commonly used known method.

Typical methods include a method in which bleach-fixing is performed after color development, followed by further washing and stabilization treatment if necessary;
If necessary, a method of further washing with water and stabilizing treatment can be applied.

As the color developing agent, various aromatic primary amine developing agents such as p-phenylene diamine type and p-amine phenol type are preferably used.

(Example) Next, the present invention will be specifically explained with reference to Examples.

Example 1 A multilayer color photographic material consisting of each layer having the composition shown below on a cellulose triacetate film support was prepared.

1st layer: Antihalation layer A gelatin solution containing black colloidal silver was added at 5Qm/m' of silver.
Two layers coated at a gelatin C of 15 g/m': Intermediate layer 2-gelatin layer containing an emulsified dispersion of 5-di-t-octylhydroquinone Third layer: Red-sensitive emulsion layer 4 mol% of iodine A silver iodobromide emulsion containing silver oxide and having an average grain size of 0.7 μm was coated with anhydro-5,5/-dichloroO-3,3 shear.
-Sulfoprobyl-9-ethyl-thiacarbonanine hydroxide pyridium salt and Ambito 0-9-ethyl-3,3-silsulfopropyl-4.5.4.15'
- 4-Hydroxy-6-methyl-1,3,3 color-sensitized red-sensitive emulsion color-sensitized with a 4:I mixture of thiacarbocyanine hydroxide triethylamine salt.
a, Diffusion-resistant cyan coupler, 1- and Droyasy-N-(
α-(2,4-di[-amylphenoxy)butyl]-
0.07 mol of 2-su7 toamide per 1 mol of silver was dissolved in tricresyl aphosphate by a conventional method, and then emulsified and dispersed in a gelatin solution.
A layer coated to give a gelatin ratio of 5.09/m'.

Layer 4: Intermediate layer 2-gelatin composition comprising an emulsified dispersion of 5-di-t-octylhydroquinone.

5th layer: Green-sensitive emulsion layer Anhydro-9-ethyl-5,5'-dichloro-3,3'-di( r-sulfopropyl)oxacarbocyanine sodium salt and anhydro-5,6゜5,'
6. '~Tetrachloro1,1'-diethyl-3,3'
- High-speed green emulsion color sensitized with a 3:1 mixture of di(gamma sulfobucovir) imidazolocarbo7anine hydroxide triethylamine salt (te.1-hydroxy-6-methyl-1,3,33,7 - Diffusion-resistant magenta coupler 7 stabilized with the addition of chitrazaindene
-(2,4,6-trichlorophenyl)-3-43-
Comparison sample to which an emulsified dispersion containing (α-(2,-1-di-t-amylphenoquine)acetamide)-penzamide]-5-pyrazolone containing 1 mol of silver (0.08 mol of silver) was added. and the counterpart of the present invention, in which an emulsified dispersion containing exemplified compound (3) in o, oos mol per mol of silver was added, respectively, were mixed with 2 and 3' l/m of silver and 2.3' l/m of gelatin, respectively.
A layer coated to give a weight of 7g/m.

6th layer; layer containing yellow colloidal colloid and 2-5-di-t-octylhydroquinone dispersion (0.1 g silver/m” gelatin 1 layer);
．． 2g/m').

7th layer: W distracting agent layer 4-hydroxy-
After adding an appropriate amount of 6-methyl-1,3,3a, 7-chitrazaindene, the diffusion-resistant yellow coupler f6. ”＋α−
[4-(1-benzyl-2-7enyl-3,5-dioxo-1,2,4-)riazolidinyl)]-]α-beverly-2-chloro5Cr-<2゜4-di-t-amylphenoxy ) butylamide] acetanilide A comparison object was added with an emulsified dispersion containing 0.22 mol per 1 mol of gold and silver, and exemplified compound (5) was added to this L'! Unexploded BA added with emulsified dispersion containing 007 mol per 1 mol
Their counterparts were respectively silver 1.0,9/m'gelatin 39/m
A layer coated to look like this.

8th layer: protective layer gelatin layer containing polymethyl methacrylate particles (average diameter 1.5 μm).

Each layer contains 2-hydroxy-4,6 gelatin as a hardening agent.
-dichloro-s-triazine sodium salt or habisu (
Vinylsulfonyl)ethane and H2 surfactants were added.

After drying the target photographic material and the photographic material of the present invention obtained as described above, they were exposed to light for MTF measurement through one layer of B, G, and R filters, and then developed as described below.

Treatment Step (38°C) Treatment Time The composition of each treatment liquid that can be used in the treatment step is as follows, for example.

[Color development reed, composition]

[Bleaching solution composition] Iron ethylenediaminetetraacetate [Fixing solution composition] [Stabilizing solution composition] The image sharpness obtained in this manner is shown in Table 1 (1 m
(M T F at 20 frequencies per peak) Table 1 There is a clear improvement effect, and although the compound according to the present invention is not added to the red sensitivity layer, it is assumed that the λITF is improved due to the irradiation prevention effect of the upper layer. Ru.

Example 2 A red 1-sensitive emulsion similar to Example 1 was used between the second and third layers of the sample of the present invention in Example 1. A red-sensing mask 1 w was coated with an emulsified dispersion containing ψ 25 moles of a hydric compound 10 per mole of saw at a ratio of 2.089 q/m of gelatin and 0.72 q/m of silver. A green-sensitive emulsion similar to that of Example 1 was provided between the fourth layer and the fifth layer of the sample of the present invention in Example 1, and 0.2 of exemplified compound (12) was added per mole of silver.
The emulsified dispersion containing 5 mol of gelatin was added to 04 g/m'
, a green-sensitive mask layer coated with silver at 0.3'i/m' was provided, and a blue mask layer similar to that in Example 1 was further provided between the 6th layer and the 7th layer of the invention O sample of Example 1. An emulsified dispersion containing 0.25 mol of exemplary compound (16) per 1 mol of silver in a sensitive emulsion was mixed with gelatin 0.69/m" and silver 0.2 g/m".
A sample of the present invention was prepared in the same manner as the sample of the present invention in Example 1, except that a light-sensitive mask layer coated to give When this was done, a clear color image was obtained.

Example 3 A multilayer color photographic material consisting of each layer having the composition shown below on a cellulose triacetate film support was prepared.

1st layer: Antihalation layer A gelatin solution containing black colloidal silver was added at 5Qm/m' of silver.
1 Gelatin 0.5! A layer coated so that it has a thickness of 1/2".

Second layer: Intermediate layer 2. Gelatin layer containing an emulsified dispersion of 5-di-t-octylhydroquinone.

Third layer: red-sensitive mask layer A silver iodobromide emulsion containing 4 mol % of silver iodide and having an average grain size of 0.7 μm is anhydro-5,5'-dichloride o o -3°3'
-r-sulfopropyl-9-ethylthiacarpocyanine hydroxide pyridylium salt anhydro-9-ethyl-3,3'-gamma-sulfoprovir-4
, 4-hydroxy-6-methyl-1,3°3a,7- in a highly sensitive red-sensitive emulsion color sensitized with a 4:1 mixture of triethylamine salt, 4-hydroxy-6-methyl-1,3°3a, 7- To the mixture stabilized by adding an appropriate amount of citrazaindene, 0.25 mol of exemplified compound (10) was added to 1 mol of silver (tricresyl phosphonic acid) (KZM).
After that, add the emulsified dispersion to the gelatin solution,
Silver 0.72 g/m”, Gelatin 2.0 g/tr
A layer coated to make it look like "i".

41st layer: low-sensitivity red-sensitive emulsion layer Example compound (10) using a silver iodobromide emulsion containing 5 mol% silver iodide and having an average grain size of 0.4 μm instead of the silver iodobromide emulsion in the third layer Instead of the crucible-diffusible cyan coupler, 1-hydroxy-N-[α-(2,4-di-t-amylphenoquine)butylcou-2-naphthamide per mole of silver,
．． 07 mol, colored cyan coupler, 1-hydroxy-4-(2-carboethoxyphenylazo)-N-Cα
-(2,4-di-t-amylphenoxy)butylcou 2
- 0.007 mol of naphthamide per mol of silver and 2-(1-phenyl-5-tetrazolylthio)-6-
[α-(2,4-di-t-amylphenoxy)acetamide] Indanone was used in the same manner as in No. 31'+3, except that 0003 mol of indanone was used per 1 mol of silver, and 2 g/m's of gelatin was added.
A layer coated to give a silver content of 1.8g/7yLt.

5th layer: high-sensitivity red-sensitive emulsion layer In place of the exemplary compound (10) in the 3rd layer, a diffusion-resistant cyan coupler, 1-hydroxy-4-ethoxycarbonylmethyloxy-N-(α-(2,4- 0.02 mol of di-t-amylphenoxy)butyl-2-naphthamide per mol of silver and 2-(1-phenyl-5-tetrazolylthio)-6-ra-(2,4-di-t-amylphenoxy) ) acetamide] indanone was applied in the same manner as the third layer, except that 1 mole of silver (0.001 mole for C was used), and the coating was applied so that gelatin was 3.0 g/m' and silver was 2.0 g/7+1'. .

Sixth layer: Intermediate layer 2. Gelatin layer containing an emulsified dispersion of 5-di-t-octylhydroquinone.

7th layer: Green-sensitive mask layer Anhydro-9-ethyl-5,57-dichloro-3,3'';-(r -sulfopropyl)oxacarbonanine sodium salt and anhydro-5,6,5',6'
-tetrachloro-1,1'-diefru 3,3'
-4-Hydroquine-4-hydroquine in a high-speed green emulsion color sensitized with a 3:1 mixture of C(r-sulfoprobyl) imidazolocarbocyanine hydroxide triethylamine salt.
Exemplary compound (12) was added to silver 1 to stabilized by adding an appropriate amount of 6-methyl-1゜3.3a,7-tetrazaindene.
A layer coated with an emulsified dispersion containing 0.25 mol/m' of silver and 0.3/m' of silver and 0.49/m' of gelatin.

8th layer: low-sensitivity green-sensitive emulsion layer In place of the silver iodobromide emulsion in the 7th layer, a silver iodobromide emulsion containing 4 mol % of total silver iodide and having an average grain size of 0.35 μm was used. Exemplary compound (12) Diffusion-resistant magenta coupler instead of 1-
(2,4,6-)dichlorophenyl)-3-(”3-(
0.08 mol of α-(2,4-di-t-amylphenoxy)acetamido)-benzamide to 5-pyrazolo per mol of silver, colored coupler, 1-(2,4,6
-)dichlorophenyl)-3-C3-(α-2,4-di-t-amylphenoxy)acetamido)penzamide]-4-(4-methoxy7phenylazo)-5-pyrazolone per 1 mole of water. 015 mol and 2-(1゛-phenyl-5-tetrazolylthio)-6-[α-(2
, 4-di-t-amylphenoxy)acetamide]indanone was used in the same manner as in the seventh layer, except that 0003 mol of silver was used.
A layer coated to give OLj/m'.

No. 9, 1: High-sensitivity green-sensitive emulsion layer Instead of exemplary compound (12) in the seventh layer, a diffusion-resistant magenta coupler, 4,4-bismethylene CI-(2,4,6
-)dichlorophenyl)-3-(3-(α-(2,4-
di-t-amylphenoxy)acetamido)-benzamido)-5-pyranolone] for 1 mole of silver: 0.
01 mole and 2-(1-phenyl-5-tetrazolylthio)-6-[α-(2,4-di-t-amylphenoxy)acetamido]indanone per mole of silver.
Gelatin 1 was prepared in the same manner as No. 7 NI except that 0.
．． 65'j/m゛, layer coated to give silver 1.597m'.

Layer 10: Yellow filter, layer containing yellow colloidal silver and 2,5-di-t-octylhydroquinone dispersion (0.1 g silver/rr? gelatin 1.29/m').

11th layer: Back mask layer 4-hydroxy-6 as a stabilizer in a highly sensitive silver iodobromide gelatin solution containing 6 mol% of silver iodide and having an average grain size of 0.8 μm.
-After adding an appropriate amount of methyl-1,3,3a,7-tetrazaindene, an emulsified dispersion containing 0.25 mol of exemplified compound (5) per mol of silver was added to gelatin 0.6 g/m", silver 0.2 so/m", a layer coated to give a silver ratio of 0.2 so/m.

12th layer: blue-sensitive emulsion layer In place of the exemplified compound (5) in the 11th layer, a yellow caprateal α-[4-(1-benzyl-2-7enyl-3.5
-dioxo-1,2,4-)riazolidinyl)]-]α
-pivalru2-chloro5-r-(2,4-di-t-
An emulsified dispersion containing 0.22 mol of amylphenoxy)butyramide]acetanilide per 1 mol of silver was added to silver log/m' gelatin 3 ji/m.
1 layer coated to give '.

Thirteenth layer: protective layer gelatin layer containing polymethyl methacrylate particles (average diameter 1.5 units).

Each layer contains 2-hydroxy-4,6 gelatin as a hardening agent.
-dichloro-5-) riazine sodium salt or bis-
(vinylsulfonyl)ethane and surfactant were added.

When the photographic material thus obtained was exposed and developed in the same manner as in Example 1, a clear color image was obtained.

(Effect of the invention) A thin film that achieves the purpose of the invention and reduces the coating film thickness of X layer.
It has become possible to provide color photographic materials with good sharpness, and it has also become possible to reduce production costs and processing costs at the same time.

Applicant: Konishiroku Photo Industry Co., Ltd.

Claims (1)

[Claims] In a light-sensitive silver halide color photographic material having a diffusion-resistant coupler in combination with a light-sensitive silver halide emulsion, said photographic material further comprises: i) formed by reaction of said diffusion-resistant coupler with an oxidized form of a color developing agent; ii) is a compound that diffuses moderately during the development process; and iii) is a compound that is capable of forming the diffusion-resistant coupler by reaction with an oxidized form of a color developing agent. A light-sensitive silver halide color photographic material characterized by containing a compound that produces a diffusion-resistant dye that is substantially the same color as the dye produced by reaction with an oxidized product of a color developing agent.